CN114566648A - PVDF lithium battery positive electrode conductive binder and preparation method of lithium battery positive electrode - Google Patents
PVDF lithium battery positive electrode conductive binder and preparation method of lithium battery positive electrode Download PDFInfo
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- CN114566648A CN114566648A CN202210130818.XA CN202210130818A CN114566648A CN 114566648 A CN114566648 A CN 114566648A CN 202210130818 A CN202210130818 A CN 202210130818A CN 114566648 A CN114566648 A CN 114566648A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 88
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 49
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000011230 binding agent Substances 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000853 adhesive Substances 0.000 claims description 28
- 230000001070 adhesive effect Effects 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 22
- -1 1-vinyl-3-butylimidazolium hexafluorophosphate Chemical compound 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 239000002608 ionic liquid Substances 0.000 claims description 10
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 8
- ARGICNMLPHJXTP-UHFFFAOYSA-N [SiH4].C(=C)C(OC(CCC)=NO)C(COC(CCC)=O)OC(CCC)=O Chemical compound [SiH4].C(=C)C(OC(CCC)=NO)C(COC(CCC)=O)OC(CCC)=O ARGICNMLPHJXTP-UHFFFAOYSA-N 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910010648 Li6CoO4 Inorganic materials 0.000 claims description 3
- 229910012946 LiV2O5 Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- UVQPDGXQIPNYNU-UHFFFAOYSA-N 1-ethenyl-3-ethyl-2h-imidazole Chemical compound CCN1CN(C=C)C=C1 UVQPDGXQIPNYNU-UHFFFAOYSA-N 0.000 claims description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- 239000011883 electrode binding agent Substances 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- FQTUOJOWQBMFTM-UHFFFAOYSA-N 1-butyl-3-ethenyl-2h-imidazole Chemical compound CCCCN1CN(C=C)C=C1 FQTUOJOWQBMFTM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of lithium batteries, in particular to a PVDF lithium battery positive electrode conductive binder and a preparation method of a lithium battery positive electrode; according to the PVDF lithium battery positive electrode conductive binder and the preparation method of the lithium battery positive electrode, monomers with different degrees of hydrophilicity and hydrophobicity are selected, the positive electrode binder for the lithium battery, which is suitable for liquid-solid two-phase interface reaction, is obtained by a chemical polymerization method, the swelling phenomenon of a positive electrode system in an electrolyte is reduced, and the active substance positive electrode current collector is not easy to lose.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a PVDF lithium battery positive electrode conductive binder and a preparation method of a lithium battery positive electrode.
Background
The choice of electrode binder material is critical to the production of high performance lithium ion batteries. Currently, the main lithium ion battery binders include PVDF, PVA, SBR and the like. PVDF is the most common positive binder, has the outstanding characteristics of strong oxidation and reduction resistance, good thermal stability and easy dispersion, but has the defects of high price and certain environmental pollution because N-methyl pyrrolidone (NMP) is used as a solvent. For different anode materials, PVDF synthesized by different methods can be applied, and meanwhile, the good effect can be achieved by combining with a corresponding homogenizing process.
CN201210286993.4 applies for a high-viscosity self-crosslinking vinylidene fluoride copolymer, a preparation method and an application thereof, and finds that double bonds capable of continuously reacting exist in an obtained polymerization product after copolymerization with VDF due to the fact that a divinyl ether compound has a unique continuous double bond structure, and can be used as a basis of a next crosslinking reaction. Further, after double-bond free radical polymerization is initiated by ultraviolet light, the cross-linking among the copolymer molecules is realized, and a cross-linked body with high bonding strength is formed.
CN105576247A discloses a modified marine polysaccharide polymer lithium ion battery binder, which is characterized in that the binder is obtained by using marine polysaccharide polymer and using monomers of acrylic acid and esters thereof as modified monomers through chemical grafting modification or physical blending modification. Compared with the prior art, the conductive adhesive has the advantages of high conductivity, high peel strength, no toxicity, greenness and environmental protection.
However, the polyvinylidene fluoride resin binder is easy to swell in the electrolyte in the positive electrode system, so that the active material falls off from the positive electrode current collector, and the discharge capacity of the lithium ion battery is rapidly reduced along with charge-discharge cycles.
Disclosure of Invention
The invention discloses a PVDF lithium battery positive electrode conductive binder and a preparation method of a lithium battery positive electrode, belonging to the technical field of lithium batteries. The invention adopts monomers with different degrees of hydrophilicity and hydrophobicity to obtain the positive adhesive for the lithium battery, which is suitable for liquid-solid two-phase interface reaction, by a chemical polymerization method.
A PVDF lithium battery positive electrode conductive binder and a preparation method of a lithium battery positive electrode are characterized by comprising the following steps:
according to the weight portion, 10-20 portions of PVDF, 0.5-3 portions of alkenyl ionic liquid, 1.5-4.5 portions of vinyl tributyrinoxime silane and 100-200 portions of N-methyl pyrrolidone are added into a reactor and evenly mixed according to the mass portion, then 0.05-0.5 portion of lithium acrylate is added, the mixture is fully and evenly stirred, cured for 20-40h, kept stand and defoamed, and then the reaction is carried out by a surface irradiation grafting method, so as to prepare the PVDF lithium battery anode conductive adhesive.
Further, the alkenyl ionic liquid cation comprises 1-vinyl-3-alkyl imidazole, 1-allyl-3-alkyl imidazole or 1-allyl-3-alkyl imidazole;
further, the alkenylionic liquid anion includes: tetrafluoroboric acid, hexafluorophosphoric acid or bistrifluoromethanesulfonylimide;
further, the alkenyl ionic liquid alkyl group includes: methyl, ethyl or butyl;
further, the alkenyl ionic liquid is selected from 1-vinyl-3-butyl imidazole bis (trifluoromethanesulfonyl) imide salt; 1-vinyl-3-butylimidazolium hexafluorophosphate; 1-vinyl-3-butylimidazolium tetrafluoroborate; 1-vinyl-3-ethylimidazole bistrifluoromethanesulfonylimide salt; 1-vinyl-3-ethylimidazole hexafluorophosphate; one or more of 1-vinyl-3-ethylimidazole tetrafluoroborate;
further, the curing temperature is 60-70 ℃;
further, the surface irradiation grafting is ultraviolet irradiation grafting, low-temperature plasma grafting or high-energy ray irradiation grafting;
further, the irradiation source used for irradiation grafting is a low-pressure mercury lamp;
further, the irradiation power mercury lamp is 100-800W;
further, the irradiation distance is 5-40 cm;
further, the irradiation time is 1-50 minutes;
further, a preparation method of the positive electrode of the PVDF lithium battery is provided:
uniformly mixing a powdery lithium battery positive electrode material with an adhesive, then pressing and forming, and drying to obtain the positive electrode of the lithium battery;
further, the cathode material is used for manufacturing a lithium battery;
furthermore, the lithium battery is round, square or angular;
further, the powdered lithium battery cathode material is selected from the group consisting of: LiCoO2、LiNiO2、LiMn2O4、LiV2O5、LiCo0.5O2、Li6CoO4；
Further, the drying condition is 100-150 ℃, and the time is 10-30 minutes.
The reaction mechanism is as follows:
monomers with different degrees of hydrophilicity and hydrophobicity are selected, a positive adhesive for a lithium battery suitable for a liquid-solid two-phase interface reaction is obtained by a chemical polymerization method, PVDF is subjected to electron beam radiation by using an electron accelerator to generate active free radicals for a grafting reaction, and the active free radicals are grafted with alkenyl ionic liquid, vinyl tributyrine oxime silane and lithium acrylate to obtain a modified PVDF adhesive.
The technical effects are as follows:
1. the swelling phenomenon of the anode system in the electrolyte is reduced, so that the active substance anode current collector is not easy to run off.
2. Has good polar organic solvent resistance characteristics such as: lithium battery electrolytes such as ethylene carbonate, propylene carbonate, gamma-butyrolactone and ethylene glycol dimethyl ether.
Drawings
FIG. 1 is an XPS broad spectrum of example 6.
Detailed Description
And (3) performance testing:
and (4) testing the electric cycle performance, and inspecting the capacity, the first effect, the cycle performance, the voltage and the rate performance of the lithium battery anode material.
The invention is further illustrated by the following specific examples:
example 1
Adding 10g of PVDF, 0.5g of 1-vinyl-3-butylimidazole bistrifluoromethanesulfonylimide salt, 1.5g of vinyl tributoxy ketoxime silane and 100g of N-methylpyrrolidone into a reactor, uniformly mixing according to mass, then adding 0.05g of lithium acrylate, fully and uniformly stirring, curing at 70 ℃ for 20h, standing for defoaming, then carrying out reaction by using a surface irradiation grafting method, wherein the power of an irradiation lamp is 600W, the irradiation distance is 20cm, and the irradiation time is 30min, thus obtaining the PVDF lithium battery positive electrode conductive adhesive.
LiCoO is used as the anode material of the lithium battery2And uniformly mixing the mixture with the prepared adhesive, then pressing and molding the mixture, and baking the mixture for 20 minutes at 120 ℃ to obtain the anode of the lithium battery.
Example 2
Adding 12g of PVDF, 1.5g of 1-vinyl-3-butylimidazole bistrifluoromethanesulfonylimide salt, 2.0g of vinyl tributoxy ketoxime silane and 120g of N-methylpyrrolidone into a reactor, uniformly mixing according to mass, then adding 0.15g of lithium acrylate, fully and uniformly stirring, curing at 70 ℃ for 20h, standing for defoaming, then carrying out reaction by using a surface irradiation grafting method, wherein the power of an irradiation lamp is 600W, the irradiation distance is 20cm, and the irradiation time is 30min, thus obtaining the PVDF lithium battery positive electrode conductive adhesive.
LiNiO serving as a powdery lithium battery cathode material2And uniformly mixing the mixture with the prepared adhesive, then pressing and molding the mixture, and baking the mixture for 20 minutes at 120 ℃ to obtain the anode of the lithium battery.
Example 3
Adding 15g of PVDF, 2.0g of 1-vinyl-3-butylimidazole hexafluorophosphate, 2.5g of vinyl tributyrinoxime silane and 150g of N-methylpyrrolidone into a reactor, uniformly mixing by mass, then adding 0.25g of lithium acrylate, fully stirring uniformly, curing for 30h at 65 ℃, standing for defoaming, then carrying out reaction by using a surface irradiation grafting method, wherein the power of an irradiation lamp is 800W, the irradiation distance is 20cm, and the irradiation time is 20min, thus preparing the PVDF lithium battery positive electrode conductive adhesive.
Preparing powdered positive electrode material LiMn of lithium battery2O4And uniformly mixing the mixture with the prepared adhesive, then pressing and molding the mixture, and baking the mixture for 20 minutes at 120 ℃ to obtain the anode of the lithium battery.
Example 4
Adding 16g of PVDF, 2.5g of 1-vinyl-3-butylimidazole tetrafluoroborate, 3.0g of vinyl tributyrinoxime silane and 160g of N-methylpyrrolidone into a reactor, uniformly mixing the materials by mass, adding 0.35g of lithium acrylate, fully and uniformly stirring the materials, curing the mixture at 65 ℃ for 30 hours, standing the mixture for defoaming, and then carrying out a reaction by using a surface irradiation grafting method, wherein the power of an irradiation lamp is 800W, the irradiation distance is 20cm, and the irradiation time is 20min to prepare the PVDF lithium battery positive electrode conductive adhesive.
Preparing a powdery lithium battery cathode material LiV2O5And uniformly mixing with the prepared adhesive, then pressing and molding, and baking at 120 ℃ for 20 minutes to obtain the anode of the lithium battery.
Example 5
Adding 18g of PVDF, 3.0g of 1-vinyl-3-butylimidazole tetrafluoroborate, 4.0g of vinyl tributyrinoxime silane and 180g of N-methylpyrrolidone into a reactor, uniformly mixing the materials by mass, adding 0.45g of lithium acrylate, fully stirring the mixture uniformly, curing the mixture at 60 ℃ for 40 hours, standing the mixture for defoaming, and then carrying out a reaction by using a surface irradiation grafting method, wherein the power of an irradiation lamp is 800W, the irradiation distance is 10cm, and the irradiation time is 15min to prepare the PVDF lithium battery anode conductive adhesive.
LiCo serving as a powdery lithium battery positive electrode material0.5O2And uniformly mixing the mixture with the prepared adhesive, then pressing and molding the mixture, and baking the mixture for 20 minutes at 120 ℃ to obtain the anode of the lithium battery.
Example 6
Adding 20g of PVDF, 3.0g of 1-vinyl-3-butylimidazolium tetrafluoroborate, 4.5g of vinyl tributyrinoxime silane and 200g of N-methylpyrrolidone into a reactor, uniformly mixing according to mass, then adding 0.5g of lithium acrylate, fully stirring uniformly, curing at 60 ℃ for 40h, standing for defoaming, then carrying out reaction by using a surface irradiation grafting method, wherein the power of an irradiation lamp is 800W, the irradiation distance is 10cm, and the irradiation time is 15min, thus obtaining the PVDF lithium battery positive electrode conductive adhesive.
The powdery lithium battery cathode material Li6CoO4And uniformly mixing the mixture with the prepared adhesive, then pressing and molding the mixture, and baking the mixture for 20 minutes at 120 ℃ to obtain the anode of the lithium battery.
Comparative example 1
When the PVDF lithium battery positive electrode conductive binder is prepared, vinyl tributyrinoxime silane is not added, and the rest is completely consistent with that of the embodiment 1.
Comparative example 2
The preparation of the PVDF lithium battery positive electrode conductive adhesive is completely consistent with that of the embodiment 1 without adding lithium acrylate. The results of the performance tests of all the above examples and comparative examples are shown in the following table:
Claims (16)
1. a PVDF lithium battery positive electrode conductive binder and a preparation method of a lithium battery positive electrode are disclosed, the operation steps are as follows:
according to the weight portion, 10-20 portions of PVDF, 0.5-3 portions of alkenyl ionic liquid, 1.5-4.5 portions of vinyl tributyrinoxime silane and 100-200 portions of N-methyl pyrrolidone are added into a reactor and evenly mixed according to the mass portion, then 0.05-0.5 portion of lithium acrylate is added, the mixture is fully and evenly stirred, cured for 20-40h, kept stand and defoamed, and then the reaction is carried out by a surface irradiation grafting method, so as to prepare the PVDF lithium battery anode conductive adhesive.
2. The PVDF lithium battery positive electrode conductive binder and the preparation method of the lithium battery positive electrode as claimed in claim 1, wherein: the alkenyl ionic liquid cation comprises 1-vinyl-3-alkyl imidazole, 1-allyl-3-alkyl imidazole or 1-allyl-3-alkyl imidazole.
3. The PVDF lithium battery positive electrode conductive binder and the preparation method of the lithium battery positive electrode as claimed in claim 1, wherein: the alkenyl ionic liquid anions include: tetrafluoroboric acid, hexafluorophosphoric acid or bistrifluoromethanesulfonylimide.
4. The preparation method of the PVDF lithium battery positive electrode conductive adhesive and the lithium battery positive electrode as claimed in claim 1, wherein the preparation method comprises the following steps: the alkenyl ionic liquid alkyl group includes: methyl, ethyl or butyl.
5. The PVDF lithium battery positive electrode conductive binder and the preparation method of the lithium battery positive electrode as claimed in claim 1, wherein: the alkenyl ionic liquid is selected from 1-vinyl-3-butyl imidazole bis (trifluoromethane) sulfonyl imide salt; 1-vinyl-3-butylimidazolium hexafluorophosphate; 1-vinyl-3-butylimidazolium tetrafluoroborate; 1-vinyl-3-ethylimidazole bistrifluoromethanesulfonylimide salt; 1-vinyl-3-ethylimidazole hexafluorophosphate; one or more of 1-vinyl-3-ethylimidazole tetrafluoroborate.
6. The PVDF lithium battery positive electrode conductive binder and the preparation method of the lithium battery positive electrode as claimed in claim 1, wherein: the curing temperature is 60-70 ℃.
7. The PVDF lithium battery positive electrode conductive binder and the preparation method of the lithium battery positive electrode as claimed in claim 1, wherein: the surface irradiation grafting is ultraviolet irradiation grafting, low-temperature plasma grafting or high-energy ray irradiation grafting.
8. The PVDF lithium battery positive electrode conductive binder and the preparation method of the lithium battery positive electrode as claimed in claim 1, wherein: the irradiation source used for the irradiation grafting is a low-pressure mercury lamp.
9. The preparation method of the PVDF lithium battery positive electrode conductive adhesive and the lithium battery positive electrode as claimed in claim 1, wherein the preparation method comprises the following steps: the irradiation power mercury lamp is 100-800W.
10. The preparation method of the PVDF lithium battery positive electrode conductive adhesive and the lithium battery positive electrode as claimed in claim 1, wherein the preparation method comprises the following steps: the irradiation distance is 5-40 cm.
11. The PVDF lithium battery positive electrode conductive binder and the preparation method of the lithium battery positive electrode as claimed in claim 1, wherein: the irradiation time is 1-50 minutes.
12. The PVDF lithium battery positive electrode conductive binder and the preparation method of the lithium battery positive electrode as claimed in claim 1, wherein: the preparation method of the positive electrode of the PVDF lithium battery is provided:
and uniformly mixing the powdery lithium battery positive electrode material with the adhesive, then pressing and forming, and drying to obtain the lithium battery positive electrode.
13. The PVDF lithium battery positive electrode conductive adhesive and the preparation method of a lithium battery positive electrode as claimed in claim 12, wherein: the cathode material is used for manufacturing a lithium battery.
14. The PVDF lithium battery positive electrode conductive adhesive and the preparation method of a lithium battery positive electrode as claimed in claim 12, wherein: the lithium battery is round, square or angular.
15. The PVDF lithium battery positive electrode conductive adhesive and the preparation method of a lithium battery positive electrode as claimed in claim 12, wherein: the powdery lithium battery positive electrode material is selected from the following components: LiCoO2、LiNiO2、LiMn2O4、LiV2O5、LiCo0.5O2、Li6CoO4。
16. The PVDF lithium battery positive electrode conductive adhesive and the preparation method of a lithium battery positive electrode as claimed in claim 12, wherein: the drying condition is 100-150 ℃, and the time is 10-30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210130818.XA CN114566648B (en) | 2022-02-12 | 2022-02-12 | PVDF lithium battery anode conductive adhesive and preparation method of lithium battery anode |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103460461A (en) * | 2011-01-27 | 2013-12-18 | 耐克森有限公司 | Binder for secondary battery cell |
| CN104140545A (en) * | 2014-05-14 | 2014-11-12 | 北京大学 | Ionic liquid/polymer electrolyte membrane and preparation method thereof |
| WO2018059492A1 (en) * | 2016-09-29 | 2018-04-05 | 比亚迪股份有限公司 | Ionic liquid polymer, preparation method therefor and application thereof |
| CN108565465A (en) * | 2018-03-26 | 2018-09-21 | 合肥国轩高科动力能源有限公司 | A kind of cyanate modified PVDF binders, anode pole piece and lithium-sulfur cell using the binder |
| JP2018160397A (en) * | 2017-03-23 | 2018-10-11 | 三洋化成工業株式会社 | Battery electrode binder |
| CN109742402A (en) * | 2019-01-08 | 2019-05-10 | 福建师范大学 | A kind of preparation method of enhancement type polyvinylidene difluoroethylene lithium battery conductive adhesive |
| CN109935833A (en) * | 2018-11-22 | 2019-06-25 | 万向一二三股份公司 | A kind of binder system of lithium battery anode slurry |
| CN113793938A (en) * | 2021-08-27 | 2021-12-14 | 成都锂能科技有限公司 | PVDF binder for lithium battery/sodium battery/potassium battery positive electrode and preparation method thereof |
-
2022
- 2022-02-12 CN CN202210130818.XA patent/CN114566648B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103460461A (en) * | 2011-01-27 | 2013-12-18 | 耐克森有限公司 | Binder for secondary battery cell |
| CN104140545A (en) * | 2014-05-14 | 2014-11-12 | 北京大学 | Ionic liquid/polymer electrolyte membrane and preparation method thereof |
| WO2018059492A1 (en) * | 2016-09-29 | 2018-04-05 | 比亚迪股份有限公司 | Ionic liquid polymer, preparation method therefor and application thereof |
| JP2018160397A (en) * | 2017-03-23 | 2018-10-11 | 三洋化成工業株式会社 | Battery electrode binder |
| CN108565465A (en) * | 2018-03-26 | 2018-09-21 | 合肥国轩高科动力能源有限公司 | A kind of cyanate modified PVDF binders, anode pole piece and lithium-sulfur cell using the binder |
| CN109935833A (en) * | 2018-11-22 | 2019-06-25 | 万向一二三股份公司 | A kind of binder system of lithium battery anode slurry |
| CN109742402A (en) * | 2019-01-08 | 2019-05-10 | 福建师范大学 | A kind of preparation method of enhancement type polyvinylidene difluoroethylene lithium battery conductive adhesive |
| CN113793938A (en) * | 2021-08-27 | 2021-12-14 | 成都锂能科技有限公司 | PVDF binder for lithium battery/sodium battery/potassium battery positive electrode and preparation method thereof |
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